Conducting Polymers Meet Lithium-Sulfur Batteries:Progress,Challenges,and Perspectives

Lithium-sulfur(Li-S)batteries have attracted increased interest because of the high theoretical energy density,low cost,and environmental friendliness.Conducting polymers(CPs),as one of the most promising materials used in Li-S batteries,can not only facilitate electron transfer and buffer the large volumetric change of sulfur benefiting from their porous structure and excellent flexibility,but also enable stronger physical/chemical adsorption capacity toward polysulfides(LiPSs)when doped with abundant heteroatoms to promote the sulfur redox kinetics and achieve the high sulfur loading.This review firstly introduces the properties of various CPs including structural CPs(polypyrrole(PPy),polyaniline(PANi),polyethylene dioxothiophene[PEDOT])and compound CPs(polyethylene oxide(PEO),polyvinyl alcohol(PVA)and poly(acrylic acid)[PAA]),and their application potential in Li-S batteries.Furthermore,the research progress of various CPs in different components(cathode,separator,and interlayer)of Li-S batteries is systematically summarized.Finally,the application perspective of the CPs in Li-S batteries as a potential guidance is comprehensively discussed.

STUDIES ON ENHANCED CONDUCTIVITY OF STRETCHED CONDUCTING POLYMERS

A physical model of series of the conductivity on chain and the interchain conductivitybetween chains is proposed to explain enhanced conductivity of stretched conducting polymers.This model suggests that the enhanced conductivity for stretched conducting polymers might bedue to increasing of the interchain conductivity between chains along the elongation direction afterdrawing processes if the conductivity on chain is assumed much larger than that of the interchainconductivity between chains. According to this model, it is expected that the temperaturedependence of conductivity measured by four-probe method for stretched conducting polymers iscontrolled by a variation of the interchain conductivity between chains with temperature, whichcan be used to explain that a metallic temperature dependence of conductivity for stretchedconducting polymers is not observed although the conductivity along the elongation direction isenhanced by two or three orders of magnitude.

INFRARED EMISSIVITY OF CONDUCTING POLYMERS

The infrared emissivity of conducting polymers in 8—20μm and at 50—150℃ in the direction of normal line has been measured as a function of wavelength, conductivity at room temperature, counterion, doping levels, measuring temperature and thickness of sample.

MEASUREMENT METHOD AND PHYSICAL MODEL OF VSC CONDUCTIVITY AND ITS APPLICATIONS IN CONDUCTING POLYMERS

Method of VSC (Voltage Shorted Compaction)can be used to determine the intrinsic temperature dependence ofconductivity ofpolycrystalline compaction. The experimental conditions and technical key for preparation of VSC device and its physical model as well as its applications in conducting polymers are discussed in detail.

A review on electronically conducting polymers for lithium-sulfur battery and lithium-selenium battery:Progress and prospects

Lithium-sulfur(Li-S) batteries and lithium-selenium(Li-Se) batteries,as environmental protection energy storage systems with outstanding theoretical specific capacities and high energy densities,have become the hotspots of current researches.Besides,elemental S(Se) raw materials are widely sourced and their production costs are both low,which make them considered one of the new generations of high energy density electrochemical energy storage systems with the most potential for development.However,poor conductivity of elemental S/Se and the notorious "shuttle effect" of lithium polysulfides(polyselenides) severely hinder the commercialization of Li-S/Se batteries.Thanks to the excellent electrical conductivity and strong absorption of lithium polysulfide(polyselenide) about electronically conducting polymer,some of the above thorny problems have been effectively alleviated.The review presents the fundamental studies and current development trends of common electronically conducting polymers in various components of Li-S/Se batteries,which involves polyaniline(PANI) polypyrrole(PPy),and polythiophene(PTh) with its derivatives,e.g.polyethoxythiophene(PEDOT) and poly(3,4-ethylene dioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS).Finally,the review not only summarizes the research directions and challenges facing the application of electronically conducting polymers,but also looks forward to the development prospects of them,which will provide a way for the practical use of electronically conducting polymers in Li-S/Se batteries with outstanding electrochemical properties in the short run.

Solution-processed wafer-scale nanoassembly of conducting polymers enables selective ultratrace nerve agent detection at low power

There is a great interest in developing microelectronic devices based on nanostructured conducting polymers that can selectively electro-couple analytes at high sensitivity and low power.Nanostructured conducting polymers have emerged as promising candidates for this technology due to their excellent stability with low redox potential,high conductivity,and selectivity endowed by chemical functionalization.However,it remains challenging to develop cost-effective and large-scale assembly approaches for functionalized conducting polymers in the practical fabrication of electronic devices.Here,we reported a straightforward waferscale assembly of nanostructured hexafluoroisopropanol functionalized poly(3,4-ethylenedioxythiophene)(PEDOT-HFIP)on smooth substrates.This approach is template-free,solution-processed,and adaptable to conductive and nonconductive substrates.By this approach,the nanostructured PEDOT-HFIPs could be easily integrated onto interdigitated electrodes with intimate ohmic contact.At the optimized space-to-volume ratio,we demonstrated a low-power,sensitive,and selective nerve agent sensing technology using this platform by detecting sarin vapor with a limit of detection(LOD)of 10 ppb and signal strength of 400 times the water interference at the same concentration,offering significant advantages over existing similar technologies.We envision that its easy scale-up,micro size,small power consumption,and combination of high sensitivity and selectivity make it attractive for various wearable platforms.

Chemically revised conducting polymers with inflammation resistance for intimate bioelectronic electrocoupling

Conducting polymers offer attractive mixed ionic-electronic conductivity,tunable interfacial barrier with metal,tissue matchable softness,and versatile chemical functionalization,making them robust to bridge the gap between brain tissue and electronic circuits.This review focuses on chemically revised conducting polymers,combined with their superior and controllable electrochemical performance,to fabricate long-term bioelectronic implants,addressing chronic immune responses,weak neuron attraction,and long-term electrocommunication instability challenges.Moreover,the promising progress of zwitterionic conducting polymers in bioelectronic implants(≥4 weeks stable implantation)is highlighted,followed by a comment on their current evolution toward selective neural coupling and reimplantable function.Finally,a critical forward look at the future of zwitterionic conducting polymers for in vivo bioelectronic devices is provided.

Recent advances and innovations in the design and fabrication of wearable flexible biosensors and human health monitoring systems based on conjugated polymers

Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing wearable biosensors have accelerated the development of point-of-care sensing platforms and implantable biomedical devices in human health care.Among numerous potential materials,conjugated polymers(CPs)are emerging as ideal choices for constructing high-performance wearable biosensors because of their outstanding conductive and mechanical properties.Recently,CPs have been extensively incorporated into various wearable biosensors to monitor a range of target biomolecules.However,fabricating highly reliable CP-based wearable biosensors for practical applications remains a significant challenge,necessitating novel developmental strategies for enhancing the viability of such biosensors.Accordingly,this review aims to provide consolidated scientific evidence by summarizing and evaluating recent studies focused on designing and fabricating CP-based wearable biosensors,thereby facilitating future research.Emphasizing the superior properties and benefits of CPs,this review aims to clarify their potential applicability within this field.Furthermore,the fundamentals and main components of CP-based wearable biosensors and their sensing mechanisms are discussed in detail.The recent advancements in CP nanostructures and hybridizations for improved sensing performance,along with recent innovations in next-generation wearable biosensors are highlighted.CPbased wearable biosensors have been—and will continue to be—an ideal platform for developing effective and user-friendly diagnostic technologies for human health monitoring.

Ignition processes and characteristics of charring conductive polymers with a cavity geometry in precombustion chamber for applications in micro/nano satellite hybrid rocket motors

The arc ignition system based on charring polymers has advantages of simple structure,low ignition power consumption and multiple ignitions,which bringing it broadly application prospect in hybrid propulsion system of micro/nano satellite.However,charring polymers alone need a relatively high input voltage to achieve pyrolysis and ignition,which increases the burden and cost of the power system of micro/nano satellite in practical application.Adding conductive substance into charring polymers can effectively decrease the conducting voltage which can realize low voltage and low power consumption repeated ignition of arc ignition system.In this paper,a charring conductive polymer ignition grain with a cavity geometry in precombustion chamber,which is composed of PLA and multiwall carbon nanotubes(MWCNT)was proposed.The detailed ignition processes were analyzed and two different ignition mechanisms in the cavity of charring conductive polymers were revealed.The ignition characteristics of charring conductive polymers were also investigated at different input voltages,ignition grain structures,ignition locations and injection schemes in a visual ignition combustor.The results demonstrated that the ignition delay and external energy required for ignition were inversely correlated with the voltages applied to ignition grain.Moreover,the incremental depth of cavity shortened the ignition delay and external energy required for ignition while accelerated the propagation of flame.As the depth of cavity increased from 2 to 6 mm(at 50 V),the time of flame propagating out of ignition grain changed from 235.6 to 108 ms,and values of mean ignition delay time and mean external energy required for ignition decreased from 462.8 to 320 ms and 16.2 to 10.75 J,respectively.The rear side of the cavity was the ideal ignition position which had a shorter ignition delay and a faster flame propagation speed in comparison to other ignition positions.Compared to direct injection scheme,swirling injection provided a more favorable flow field environment in the cavity,which was beneficial to ignition and initial flame propagation,but the ignition position needed to be away from the outlet of swirling injector.At last,the repeated ignition characteristic of charring conductive polymers was also investigated.The ignition delay time and external energy required for ignition decreased with repeated ignition times but the variation was decreasing gradually.

Nanoscale engineering of conducting polymers for emerging applications in soft electronics

Soft electronics featuring exceptional mechanical compliance and excellent electrical performance hold great promise for applications in soft robotics,artificial intelligence,bio-integrated electronics,and wearable electronics.Intrinsically stretchable and conductive materials are crucial for soft electronics,enabling large-area and scalable fabrication,high device density,and good mechanical compliance.Conducting polymers are inherently stretchable and conductive.They can be precisely synthesized from vastly available building blocks,and thus they provide a fruitful platform for fabricating soft electronics.However,amorphous bulk-phase conducting polymers typically exhibit poor mechanical and electrical characteristics.Consequently,it is highly desirable to develop novel engineering approaches to overcome the intrinsic limitations of conducting polymers.In recent years,numerous engineering strategies have been developed to enhance their performances in soft electronic devices via constructing various nanostructures.In this review,we first summarize several unique methodologies to fabricate conducting polymer-based nanostructures.We then discuss how nanoscale engineering approaches can improve several crucial parameters,including electrical conductivity,stretchability,sensitivity,and self-healing property of conducting polymers.Moreover,we also discuss device-level integration of conducting polymer-based nanostructures with other materials for applications in skin-inspired electronics and bio-integrated electronics.Finally,we provide perspectives on challenges and future directions in engineering nanostructured conducting polymers for soft electronics.

Semiconducting covalent organic frameworks:a type of two-dimensional conducting polymers

In recent years,as a new class of two-dimensional polymer,covalent organic frameworks（COFs） have attracted intensive attention and developed rapidly.This review provides an overview of a type of COFs which can be utilized as organic semiconductors.Carefully choosing monomers as the building blocks will bestow different types of semiconducting character on COFs.We summarize the p-type,n-type and ambipolar semiconducting COFs and highlight the effects of π-functional building blocks on the photoconductive behaviors of the semiconducting COFs.

Capacitance Performances of Supramolecular Hydrogels Based on Conducting Polymers

The capacitance performances of poly（3,4-ethylenedioxythiophene）-poly（styrenesulfonate）（PEDOT-PSS） supramolecular hydrogels have been investigated systematically. The materials show a specific capacitance of 67 F/g and display excellent rate capability at the scan rate as high as 5000 m V/s in the cyclic voltammogram measurements, accompanied by good cycle stability. On the basis of the measurements of the microscale morphologies, specific areas and electrical conductivities, the mechanisms for the improvement of the electrochemical properties are discussed and ascribed to the novel porous microstructures of the hydrogels and the synergetic effect of the rigid PEDOT and soft PSS components. Furthermore, polyaniline（PAn） is compounded with the PEDOT-PSS hydrogels through an interfacial polymerization process, endowing the hydrogel materials with a higher specific capacitance of 160 F/g at the scan rate of 5000 m V/s. The significance of this work lies in the demonstration of a novel method to solve the problems of conducting polymers in electrochemical applications.

Enhanced Growth and Redox Characteristics of Some Conducting Polymers on Carbon Nanotube Modified Electrodes

1 Results Recent studies on the electrochemistry of a number of active compounds at carbon nanotube electrodes have proved beyond doubt their excellent electrocatalytic properties.Particularly,the advancements accomplished towards the functionalization of carbon nanotubes resulting in their enhanced solubilization in aqueous solutions have helped in the preparation of stable carbon nanotube electrodes.Glassy carbon has been invariably the preferred substrate for casting carbon nanotube electrodes.Such c...

Application of intrinsically conducting polymers in flexible electronics

Intrinsically conducting polymers(ICPs),such as polyacetylene,polyaniline,polypyrrole,polythiophene,and poly(3,4-ethylenedioxythiophene)(PEDOT),can have important application in flexible electronics owing to their unique merits including high conductivity,high mechanical flexibility,low cost,and good biocompatibility.The requirements for their application in flexible electronics include high conductivity and appropriate mechanical properties.The conductivity of some ICPs can be enhanced through a postpolymerization treatment,the so-called“secondary doping.”A conducting polymer film with high conductivity can be used as flexible electrode and even as flexible transparent electrode of optoelectronic devices.The application of ICPs as stretchable electrode requires high mechanical stretchability.The mechanical stretchability of ICPs can be improved through blending with a soft polymer or plasticization.Because of their good biocompatibility,ICPs can be modified as dry electrode for biopotential monitoring and neural interface.In addition,ICPs can be used as the active material of strain sensors for healthcare monitoring,and they can be adopted to monitor food processing,such as the fermentation,steaming,storage,and refreshing of starch-based food because of the resistance variation caused by the food volume change.All these applications of ICPs are covered in this review article.

Vapor Phase Polymerization Deposition Conducting Polymer Nanocomposites on Porous Dielectric Surface as High Performance Electrode Materials

We report chemical vapor phase polymerization(VPP) deposition of poly(3,4-ethylenedioxythiophene)(PEDOT) and PEDOT/graphene on porous dielectric tantalum pentoxide(Ta_2O_5) surface as cathode films for solid tantalum electrolyte capacitors. The modified oxidant/oxidant-graphene films were first deposited on Ta_2O_5 by dip-coating, and VPP process was subsequently utilized to transfer oxidant/oxidant-graphene into PEDOT/PEDOT-graphene films. The SEM images showed PEDOT/PEDOT-graphene films was successfully constructed on porous Ta_2O_5 surface through VPP deposition, and a solid tantalum electrolyte capacitor with conducting polymer-graphene nano-composites as cathode films was constructed. The high conductivity nature of PEDOT-graphene leads to resistance decrease of cathode films and lower contact resistance between PEDOT/graphene and carbon paste. This nano-composite cathode films based capacitor showed ultralow equivalent series resistance(ESR) ca. 12 m? and exhibited excellent capacitance-frequency performance, which can keep 82% of initial capacitance at 500 KHz. The investigation on leakage current revealed that the device encapsulation process has no influence on capacitor leakage current, indicating the excellent mechanical strength of PEDOT/PEDOT-gaphene films. This high conductivity and mechanical strength of graphene-based polymer films shows promising future for electrode materials such as capacitors, organic solar cells and electrochemical energy storage devices.

Current-voltage characteristics of individual conducting polymer nanotubes and nanowires

We report the current-voltage （I-V） characteristics of individual polypyrrole nanotubes and poly（3,4- ethylenedioxythiophene） （PEDOT） nanowires in a temperature range from 300 K to 2 K. Considering the complex structures of such quasi-one-dimensional systems with an array of ordered conductive regions separated by disordered barriers, we use the extended fluctuation-induced tunneling （FIT） and thermal excitation model （Kaiser expression） to fit the temperature and electric-field dependent I-V curves. It is found that the I-V data measured at higher temperatures or higher voltages can be well fitted by the Kaiser expression. However, the low-temperature data around the zero bias clearly deviate from those obtained from this model. The deviation （or zero-bias conductance suppression） could be possibly ascribed to the occurrence of the Coulomb-gap in the density of states near the Femi level and/or the enhancement of electron-electron interaction resulting from nanosize effects, which have been revealed in the previous studies on low-temperature electronic transport in conducting polymer films, pellets and nanostructures. In addition, similar I--V characteristics and deviation are also observed in an isolated K0.27MnO2 nanowire.

Alcohol-dispersed polymer complex as an effective and durable interface modifier for n-i-p perovskite solar cells

Abundant interfacial defects remain a significant challenge that hampers both the efficiency and stability of perovskite solar cells(PSCs).Herein,an alcohol-dispersed conducting polymer complex,denoted as PEDOT:F(Poly(3,4-ethylene dioxythiophene):Perfluorinated sulfonic acid ionomers),is introduced into the interface between perovskite and hole transporting layer in regular-structured PSCs.PEDOT:F serves as a multi-functional interface layer(filling grain boundaries and covering perovskite's grain-surface)to achieve a robust interaction with organic groups within perovskites,which could induce a structural transformation of PEDOT to increase its conductivity for the efficient hole-transport.Furthermore,the strong interaction between PEDOT and perovskites could promote an effective coupling of undercoordinated Pb~(2+)ions with the lone electron pairs near O&S atoms in PEDOT molecules,thereby enhancing defect passivation.Additionally,PEDOT:F with inherent hydrophobic properties prevents effectively moisture invasion into perovskites for the improved long-term stability of the PSCs.Consequently,the PEDOT:F-based PSCs achieved a champion efficiency of 24.81%,and maintained ca.92%of their initial efficiency after 7680 h of storage in a dry air environment,accompanied by the enhanced photothermal stability.

Highly Elastic,Bioresorbable Polymeric Materials for Stretchable,Transient Electronic Systems

Substrates or encapsulants in soft and stretchable formats are key components for transient,bioresorbable electronic systems;however,elastomeric polymers with desired mechanical and biochemical properties are very limited compared to nontransient counterparts.Here,we introduce a bioresorbable elastomer,poly(glycolide-co-ε-caprolactone)(PGCL),that contains excellent material properties including high elongation-at-break(<1300%),resilience and toughness,and tunable dissolution behaviors.Exploitation of PGCLs as polymer matrices,in combination with conducing polymers,yields stretchable,conductive composites for degradable interconnects,sensors,and actuators,which can reliably function under external strains.Integration of device components with wireless modules demonstrates elastic,transient electronic suture system with on-demand drug delivery for rapid recovery of postsurgical wounds in soft,time-dynamic tissues.

Recent progress and future research directions for electrochromic zinc-ion batteries

In recent times,future energy storage systems demand a multitude of functionalities beyond their traditional energy storage capabilities.In line with this technological shift,there is active research and development of electrochromic-energy storage systems designed to visualize electrochemical charging and discharging processes.The conventional electrochromic-energy storage devices primarily integrated supercapacitors,known for their high power density,to enable rapid color contrast.However,the low energy density of supercapacitors restricts overall energy storage capacity,acting as a significant barrier to expanding the application range of such systems.In this review,we introduce electrochromic zinc(Zn)-ion battery systems,which effectively overcome the limitation of low energy density,and provide illustrative examples of their applicability across diverse fields.Although many recent research works are present for electrochromic Zn-ion batteries,little review has so far taken place.Our objective is to discuss on the current progress and future directions for electrochromic Zn-ion batteries,which are applicable for wearable electronics applications and energy storage systems.This review provides an initial milestone for future researchers in electrochromic energy storage and zinc-ion batteries,which will lead to a stream of future works related to them.